Note: Descriptions are shown in the official language in which they were submitted.
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Stabilized Articles
The present invention relates to non-agricultural articles which keep their
properties during
the use and degrade later on, until total disintegration and disappearance of
the plastic. The
invention further relates to a method for controlling the weathering
resistance and the
degradation of non-agricultural articles. The desired effect is obtained with
specific
combinations of degradant metal salts and stabilizers.
A brief description of some exemplary non-agricultural articles made in
accordance with the
invention follows. Typically, the articles are required to have a relatively
long service life
followed by a relatively short period during which embrittlement and
fragmentation occurs,
either in situ or in a landfill. The articles may be film products comprising
polyolefins or other
organic polymers.
(a) Geotextiles. These are films, woven or spun-bonded fabrics that are used
in civil
engineering projects, primarily for temporary soil stabilization. In road and
bridge building
operations, for example, it is necessary that soil embankments and road base
materials
be stabilized and consolidated until trees, brushes and grass become
established,
typically for periods of six to eighteen months. Likewise, ditches and other
drainage
devices require temporary consolidation. When the service requirements are
over, the
material can degrade and be assimilated harmlessly into the surrounding
environment.
(b) Multiple-use landfill covers. These can be used to cover a landfill active
face overnight,
pulled off in the morning and re-deployed at the end of the day. After some
weeks,
mechanical damage requires that the thick film cover be replaced. The pieces
of the old
cover can then undergo oxo-biodegradation after burial in the landfill.
(c) Industrial covers. Such covers, including tarpaulins and pallet wraps, are
frequently
required to provide protection for weeks or months and are then discarded
after
mechanical damage has rendered them no longer useful. Such covers wilt degrade
in a
landfill if made in accordance with the present invention. Other industrial
covers in
accordance with the invention include the wrappings for kiln-dried lumber, for
new cars
and boats during storage and transportation; temporary enclosures for
buildings during
repairs (for example, leaky condos) seasonal outdoor displays; covers for
mining
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applications and oil rig applications, to cover and protect the work areas for
the period of
the year when the work cannot be done; covers for mothballing applications,
for covering
equipment such as chemical or oil industry equipment that has to be preserved
for a time
when not in use. All such covers and wrappings made in accordance with the
invention
can be disposed of in landfills after their service life and then undergo
degradation.
(d) Waste covers, including covers and liners used in the construction or
operation of a
landfill. These have a service life that may be from several days to several
months,
depending upon the application. After their service life, they can degrade in
the landfill.
(e) Temporary scaffolding sheets. These are used in the construction industry
to protect
inside surfaces during repairs. Their service life is typically between about
three and
eight months. After their service life, they can be disposed of and degrade in
a landfill.
(f) Building films. These are used to protect some parts of a building during
construction or
repairs. Their service life is typically between two months and one year.
(g) Silt fences. These are used to protect temporarily some repair work or
construction done
on highways, fences, etc. Their service life is typically up to about one
year.
(h) Flexible packaging wraps. These are used in the lumber and steel
industries to protect
lumber and metal goods during transportation and storage.
(i) Poultry curtains, made of polymer films. These are used in poultry farms
to build
temporary walls.
(j) Films for building temporary shelter constructions, such as emergency
shelters.
In all of the foregoing examples, the non-agricultural article, made in
accordance with the
invention, will keep its properties during use and will degrade after its
service life.
The invention also relates to a method for controlling the weather resistance
and the
degradation of a non-agricultural organic polymer article, for example
articles of the types
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described above, which comprises incorporating into the organic polymer
components (II)
and (III) as defined below.
The invention also relates to a composition comprising components (II) and
(III), and
optionally one or more of components (IV), (V), (VI), (VII) or (VIII) as
defined below, for .
incorporation with an organic polymer to form a non-agricultural article.
The invention also relates to the use of a mixture containing components (II)
and (III), and
optionally one or more of components (IV), (V), (VI), (VII) or (VIII) as
defined below, for
controlling the weathering resistance and the degradation of a non-
agricultural organic
polymer article.
The non-agricultural article of the present invention comprises an organic
polymer, an
organic salt of Fe, Ce, Co, Mn, Cu or Vd and one or more sterically hindered
amine
compounds.
Shelf stable nonwoven fabrics and films are disclosed in US-A-5,393,831. A
method for
controlling the degradation start time is further disclosed in JP-A-05/043749.
Chemically
degradable polyolefin films are also described in US-A-5,565,503.
Stabilized plastics are for example described in EP-A-226,453, GB-A-1,582,280,
US-A-3,909,333, US-A-5,859,098, DE-A-4,003,129 and EP-A-172,691.
The present invention relates in particular to a non-agricultural article
comprising the
components
(I) an organic polymer,
(II) an organic salt of Fe, Ce, Co, Mn, Cu or Vd, and
(III) one or more sterically hindered amine compounds selected from the group
consisting
of
a compound of the formula (A-1 )
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CH3
-CHz ~H- (A-1 )
A~
CH3
1
wherein
A, is hydrogen or C,-C4alkyl,
AZ is a direct bond or C,-C,oalkylene, and
n, is a number from 2 to 50;
at least one compound of the formulae (A-2-a) and (A-2-b)
H3C CH3 CH
2
~(CH2)9
CH2 CH-CH2 N CH2 (A-2-a)
~N
OH H3C CH3 IIO
nz
HZ
/CH2
(CHz)s / I N
~CHZ O O
H3C ~CH3 (A-2-b)
H3C i CH3
H
- ~z
wherein
n2 and n2* are a number from 2 to 50;
a compound of the formula (A-3)
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H3C CH3
O A H3C CHI
0
H N O Aa
N - CHi - H-CHx N ~ O HOC CHs OH O H3C CH
HaC CH ~ N - CH2 - H-CHz N I '
a O OH H C N CHz CH- CHZ - N
s CH3 O OH A~ -~~~ N H
HOC CH3 '~'a O
3 ~ HsC CH3
Aa Aa n3
(A-3)
wherein
A3 and A4 independently of one another are hydrogen or C,-Cealkyl, or A3 and
A4 together
form a C2-C,4alkylene group, and
the, variables n3 independently of one another are a number from 1 to 50;
a compound of the formula (A-4)
As
CHz ~ CHZ- ~ H (A-4)
-o I-o
Ae A~ na
wherein
n4 is a number from 2 to 50,
AS is hydrogen or C,-C4alkyl,
the radicals A6 and A, independently of one another are C,-C4alkyl or a group
of the formula
(a-I)
H3C CH3
N As (a-I)
H3C CH3
wherein Ae is hydrogen, C,-Csalkyl, -O', -OH, -CHZCN, C,-C,Balkoxy, C2-
C,Balkoxy substituted
by -OH; C5-C,2cycloalkoxy, C3-Cfialkenyl, C,-C9phenylalkyl unsubstituted or
substituted on
the phenyl by 1, 2 or 3 C,-C4alkyl; or C,-Ceacyl,
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with the proviso that at least 50 % of the radicals A~ are a group of the
formula (a-I);
a compound of the formula (B-1 )
HsC CHs
(B 1 )
E~ N O-C Ez
H3C ~CH3 m 1
in which
E, is hydrogen, C,-Csalkyl, -O', -OH, -CHZCN, C,-C,salkoxy, C2-C~8alkoxy
substituted by -OH;
Cs-Cl2cycloalkoxy, C3-Csalkenyl, C~-C9phenylalkyl unsubstituted or substituted
on the phenyl
by 1, 2 or 3 C,-C4alkyl; or C,-Ceacyl,
m~isl,2or4,
if m, is 1, Ez is C,-C2salkyl,
if m, is 2, E2 is C,-C,4alkylene or a group of the formula (b-I)
Es
C - E4 ~ ~ ~H (b-I)
I
Ea
Es
wherein E3 is C,-C,oalkyl or C2-C~oalkenyl, E4 is C,-C,oalkylene, and
Es and Es independently of one another are C,-C4alkyl, cyclohexyl or
methylcyclohexyl, and
if m, is 4, E2 is C4-Cloalkanetetrayl;
a compound of the formula (B-2)
H2C CH CH CH2 (B-2)
E~ E~ E~ E~
in which
two of the radicals E, are -COO-(C,-CZOalkyl), and
two of the radicals E~ are a group of the formula (b-II)
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HsC CH3
COO N-E8 (b-
H3C CH3
with E8 having one of the meanings of E,;
a compound of the formula (B-3)
Eio /E»
E~N (B-3)
O C=O
H3C I /CH3
H3C I CH3
E~2
in which
E9 and E,o together form C2-C,4alkylene,
E" is hydrogen or a group -Z,-COO-Z2,
Z, is CZ-C,Qalkylene, and
Zz is C,-C24alkyl, and
E,2 has one of the meanings of E,;
a compound of the formula (B-4)
H3C CH3 E~4 O E H3C CH3
4
E~3-N N-E~5-C-N N-E~3 (B-4)
H3C CH3 H3C CH3
wherein
the radicals E,3 independently of one another have one of the meanings of E,,
the radicals E,4 independently of one another are hydrogen or C,-C,Zalkyl, and
E,5 is C,-C,oalkylene or C3-C,oalkylidene;
a compound of the formula (B-5)
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_g_
HsC CHa
O
N J .N - E~s (B_5)
H3C CH3 N
N H3C CH3
Eis N NON
O
HaC CHs
wherein
the radicals E,s independently of one another have one of the meanings of E,;
a compound of the formula (B-6)
E O H3C CH3
i~
~N N-E~s (B-6)
v \
O H3C CH3
in which
E" is C,-C24alkyl, and
E,$ has one of the meanings of E,;
a compound of the formula (B-7)
0
E~9~ ~ /Ez~ (B-
N- _N
O'/ N \'
O
Eza
in which
E,9, E2o and E2, independently of one another are a group of the formula (b-
III)
H3C CH3
CHZ CH-CH2 NH N-Ezz (b-III)
OH
H3C CH3
wherein E22 has one of the meanings of E,;
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a compound of the formula (B-8)
O HsC CH3
C-O N-Ezs
H3C CH3
CH - C (B-
HsC CHs
Eza
C-O N-Ezs
O H3C CH3
wherein
the radicals E23 independently of one another have one of the meanings of E,,
and E24 is hydrogen, C~-C,2alkyl or C1-Ci2alkoxy;
a compound of the formula (B-9)
O
H3C \
EZ5 N N Eas (B-g)
H3C CH3 m
2
wherein
m2 is 1, 2 or 3,
E25 has one of the meanings of E,, and
when mz is 1, E26 is a group -CH2CH2 NH--~ ,
when m2 is 2, E2s is C2-C22alkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
i za
Eze
-Ezi N ~ N ~ N -Ezi
N ~ N (b-I V)
i -Ez~
Eza
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wherein the radicals E2, independently of one another are CZ-C,2alkylene, and
the radicals E28 independently of one another are C,-C,zalkyl or CS-
C,2cycloalkyl;
a compound of the formula (B-10)
0 0
H3C CH3 ~ ~ ~ ~ H3C CH3
CH CH
E29 - N N - E3o - N N E29 (B-10)
H3C CH3 H3C CH3
wherein
the radicals E29 independently of one another have one of the meanings of E,,
and
E3o is C2-C22alkylene, C5-C,cycloalkylene, C,-C4alkylenedi(C5-
C,cycloalkylene), phenylene or
phenylenedi(C,-C4alkylene);
a compound of the formula (C-1 )
N
N-Rz N~ (C-1 )
N~ N
R R
-Rs
R< b
1
in which
R,, R3, R4 and R5 independently of one another are hydrogen, C,-C,Zalkyl, CS-
C,2cycloalkyl,
C,-C4-alkyl-substituted C5-C,2cycloalkyl, phenyl, phenyl which is substituted
by -OH and/or
C,-C,oalkyl; C,-C9phenylalkyl, C,-C9phenylalkyl which is substituted on the
phenyl radical by
-OH and/or C,-C,oalkyl; or a group of the formula (c-I)
HsC CH3
~N-R6 (C-I)
H3C CH3
R2 is C2-C,8alkylene, C5-C,cycloalkylene or C,-C4alkylenedi(CS-
C,cycloalkylene),
or
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the radicals R,, R2 and R3, together with the nitrogen atoms to which they are
bonded, perform a 5- to 10-membered heterocyclic ring, or
R4 and R5, together with the nitrogen atom to which they are bonded, form a 5-
to
10-membered heterocyclic ring,
R6 is hydrogen, C,-CBalkyl, -O', -OH, -CH2CN, C,-C,ealkoxy, C2-C,$alkoxy
substituted by -OH;
C5-C,2cycloalkoxy, C3-Csalkenyl, C,-C9phenylalkyl unsubstituted or substituted
on the phenyl
by 1, 2 or 3 C,-C4alkyl; or C,-Csacyl, and
b, is a number from 2 to 50,
with the proviso that at least one of the radicals R,, R3, R4 and R5 is a
group of the
formula (c-I);
a compound of the formula (C-2)
X~N~N Re N R9 N Rio i -~N~~ --Xa
N~ ~~N ~ ~ R N~ N
' N~ N N~ N
~ ~ X
~N~ ~N~
Xs Xa Xs Xs
(C-2)
wherein
R, and R" independently of one another are hydrogen or C,-C,2alkyl,
R8, R9 and R,o independently of one another are C2-C,oalkylene, and
X,, X2, X3, X4, X5, X6, X, and X8 independently of one another are a group of
the formula
(c-I I),
H3C CH3
N-R~s (C-II)
R'2 H3C CH3
in which R,2 is hydrogen, C,-C,zalkyl, CS-C,2cycloalkyl, C,-C4alkyl-
substituted
CS-C,2cycloalkyl, phenyl, -OH- and/or C,-C,oalkyl-substituted phenyl, C,-
C9phenylalkyl,
C,-C9phenylalkyl which is substituted on the phenyl radical by -OH and/or C,-
C,oalkyl; or a
group of the formula (c-I) as defined above, and
R,3 has one of the meanings of R6;
a compound of the formula (C-3)
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(C-3)
3
CH3
's J b
2
in which
R,4 is C,-C,oalkyl, CS-C,zcycloalkyl, C,-C4alkyl-substituted CS-C,zcycloalkyl,
phenyl or
C,-C,oalkyl-substituted phenyl,
R,5 is C3-C,oalkylene,
R,6 has one of the meanings of R6, and
b2 is a number from 2 to 50;
a compound of the formula (C-4)
Rzo Rza
~~CHz C CHz i (C-4)
p i C R~s p i O Rzs
R1~ ~ zi
Rzz
H3C I /CH3
HsC i CH3
- Ris b3
in which
R" and Rz, independently of one another are a direct bond or a -N(Xs)-CO-X,o-
CO-N(X")-
group, where Xs and X" independently of one another are hydrogen, C,-Cealkyl,
C5-C,zcycloalkyl, phenyl, C,-Csphenylalkyl or a group of the formula (c-I),
X,o is a direct bond or C,-C4alkylene,
R,8 has one of the meanings of R6,
R,s, Rzo, Rz3 and Rz4 independently of one another are hydrogen, C,-C3oalkyl,
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CS-C,2cycloalkyl or phenyl,
R22 is hydrogen, C,-C3oalkyl, CS-C,2cycloalkyl, phenyl, C,-C9phenylalkyl or a
group of the
formula (c-I), and
b3 is a number from 1 to 50;
a compound of the formula (C-5)
II II o 0
C-R25 C,H R26 ~H-R2~ C-O-R2~ ~ >-Rzs O
_I O O
O I i-O
O O
H3C I /CH3 H3C I /CH3
H3C N~CH3 H3C i ~CH
3
Rao Rao
4
(C-5)
in which
RzS, R2s, R2,, R2s and R29 independently of one another are a direct bond or
C,-C,oalkylene,
R3o has one of the meanings of R6, and
b4 is a number from 1 to 50; and
a product (C-6) obtainable by reacting a product, obtained by reaction of a
polyamine of the
formula (C-6-1 ) with cyanuric chloride, with a compound of the formula (C-6-
2)
HZN (CHZ) , NH (CH2) " NH (CH2) ", NH2 (C-6-1 )
b5 b 5 b 5
H-N R3~ (C-6-2)
HsC CHs
HsC i CH3
Rs2
in which
b'S, b"5 and b"'S independently of one another are a number from 2 to 12,
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R3, is hydrogen, C,-C,2alkyl, C5-C,2cycloalkyl, phenyl or C,-C9phenylalkyl,
and
R32 has one of the meanings of R6.
When the non-agricultural article according to the present invention contains
a polyolefin, the
presence of an oxidizable unsaturated compound, in particular natural rubber,
styrene
butadiene resin, fat or oil, is preferably disclaimed.
A non-agricultural article which is free of an oxidizable unsaturated
compound, in particular
natural rubber, styrene butadiene resin, fat or oil, is of special interest.
Examples of alkyl having up to 30 carbon atoms are methyl, ethyl, propyl,
isopropyl, n-butyl,
sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-
methylpentyl, 1,3-dimethyl-
butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-
methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-
tetramethylpentyl, nonyl,
decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl and triacontyl.
One of the
preferred definitions of A8, E~, Ee, E,2, E,3, E,6, E,e, E22, Ezs, Ezs, Ezs,
Rs, R,3, R,s, R,a, Rao
and R32 is C,-C4alkyl, especially methyl. R3, is preferably butyl.
Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy,
isopropoxy,
butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy,
dodecyloxy,
tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of
E, is
octoxy. E24 is preferably C,-C4alkoxy and one of the preferred meanings of R6
is propoxy.
Examples of C5-C,2cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl and
cyclododecyl. C5-CeCycloalkyl, especially cyclohexyl, is preferred.
C,-C4AIkyl-substituted C5-C,2cycloalkyl is for example methylcyclohexyl or
dimethylcyclohexyl.
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Examples of CS-C,2cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy,
cyclooctoxy,
cyclodecyloxy and cyclododecyloxy. C5-CeCycloalkoxy, in particular
cyclopentoxy and
cyclohexoxy, is preferred.
-OH- and/or C,-C,oalkyl-substituted phenyl is for example methylphenyl,
dimethylphenyl,
trimethylphenyl, tent-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
Examples of C,-C9phenylalkyl are benzyl and phenylethyl.
C,-C9Phenylalkyl which is substituted on the phenyl radical by -OH and/or by
alkyl having up
to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl,
trimethylbenzyl, tert-
butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl,
butenyl, pentenyl
and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably
saturated.
Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl,
propionyl,
butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and
benzoyl.
C,-CBAlkanoyl, C3-Caalkenyl and benzoyl are preferred. Acetyl and acryloyl are
especially
preferred.
Examples of alkylene having up to 22 carbon atoms are methylene, ethylene,
propylene,
trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene,
hexamethylene,
trimethylhexamethylene, octamethylene and decamethylene.
i Ha
An example of C3-C,oalkylidene is the group -C- ,
CH3
An example of C4-C,oalkanetetrayl is 1,2,3,4-butanetetrayl.
An example of C5-C,cycloalkylene is cyclohexylene.
An example of C,-C4alkylenedi(CS-C,cycloalkylene) is methylenedicyclohexylene.
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An example of phenylenedi(C~-C4alkylene) is methylene-phenylene-methylene or
ethylene-phenylene-ethylene.
Where the radicals R,, R2 and R3, together with the nitrogen atoms to which
they are
attached, form a 5- to 10-membered heterocyclic ring, this ring is for example
i Ha
H2 \ 2 % HZ
~N , \ /N
CH2 CH2 CH2 CH2
A 6-membered heterocyclic ring is preferred.
Where the radicals R4 and R5, together with the nitrogen atom to which they
are attached,
form a 5- to 10-membered heterocyclic ring, this ring is for example 1-
pyrrolidyl, piperidino,
morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-
trimethyl-1-
homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is
particularly
preferred.
One of the preferred definitions of R,9 and Rz3 is phenyl.
R26 is preferably a direct bond.
n~, n2, nZ* and n4 are preferably a number from 2 to 25, in particular 2 to
20.
n3 is preferably a number from 1 to 25, in particular 1 to 20 or 2 to 20.
b, and b2 are preferably a number from 2 to 25, in particular 2 to 20.
b3 and b4 are preferably a number from 1 to 25, in particluar 1 to 20 or 2 to
20.
b'S and b"'S are preferably 3 and b"5 is preferably 2.
Ae is preferably hydrogen, C,-C4alkyl, C~-C,oalkoxy, cyclohexyloxy, allyl,
benzyl or acetyl.
E,, Ee, E,2, E,3, E~6, E,B, E22, E2s, Ezs and E29 are preferably hydrogen, C,-
C4alkyl,
C,-C,oalkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
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Rs~ R,a~ R,s~ RlBr Rso and R3z are preferably hydrogen, C,-C4alkyl, C,-
C,oalkoxy,
cyclohexyloxy, allyl, benzyl or acetyl.
Aa~ E,~ Ea~ E,2~ E,a~ E,s~ E,a~ Ez2~ E2s~ Ezs, Ezs~ Rs~ Rl3r R,s~ R,s, Rso and
R32 are preferably
hydrogen or methyl and E~ and Rs additionally are C,-Cealkoxy.
The compounds described above as component (III) are essentially known and
commercially available. All of them can be prepared by known processes.
The preparation of the compounds of the formulae (A-1), (A-2-a), (A-2-b), (A-
3)
and (A-4) is disclosed, for example, in US-A-4,233,412, US-A-4,340,534,
WO-A-98/51,690 and EP-A-1,803.
The preparation of the compounds of the formulae (B-1 ), (B-2), (B-3), (B-4),
(B-5),
(B-6), (B-7), (B-8), (B-9) and (B-10) is disclosed, for example, in US-A-
5,679,733,
US-A-3,640,928, US-A-4,198,334, US-A-5,204,473, US-A-4,619,958,
US-A-4,110,306, US-A-4,110,334, US-A-4,689,416, US-A-4,408,051,
SU-A-768,175 (Derwent 88-138,751/20), US-A-5,049,604, US-A-4,769,457,
US-A-4,356,307, US-A-4,619,956, US-A-5,182,390, GB-A-2,269,819,
US-A-4,292,240, US-A-5,026,849, US-A-5,071,981, US-A-4,547,538 and
US-A-4,976,889.
The preparation of the compounds of the formulae (C-1 ), (C-2), (C-3), (C-4)
and
(C-5) as well as the product (C-6) is disclosed, for example, in US-A-
4,086,204,
US-A-6,046,304, US-A-4,331,586, US-A-4,108,829, US-A-5,051,458,
WO-A-94/12,544 (Derwent 94-177,274/22), DD-A-262,439 (Derwent
89-122,983/17), US-A-4,857,595, US-A-4,529,760 and US-A-4,477,615 and CAS
136,504-96-6.
The product (C-6) can be prepared analogously to known processes, for example
by reacting a polyamine of formula (C-6-1 ) with cyanuric chloride in a molar
ratio of
from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium
carbonate
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or potassium carbonate in an organic solvent such as 1,2-dichloroethane,
toluene,
xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from -
20°C to
+10°C, preferably from -10°C to +10°C, in particular from
0°C to +10°C, for from 2
to 8 hours, followed by reaction of the resultant product with a 2,2,6,6-
tetramethyl-
4-piperidylamine of the formula (C-6-2). The molar ratio of the 2,2,6,6-
tetramethyl-
4-piperidylamine to polyamine of the formula (C-6-1 ) employed is for example
from
4:1 to 8:1. The quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be
added
in one portion or in more than one portion at intervals of a few hours.
The molar ratio of polyamine of the formula (C-6-1 ) to cyanuric chloride to
2,2,6,6-
tetramethyl-4-piperidylamine of the formula (C-6-2) is preferably from 1:3:5
to
1:3:6.
The following example indicates one way of preparing a preferred product (C-6-
a).
Example: 23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) of N,N'-
bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrous potassium
carbonate are reacted at 5°C for 3 hours with stirring in 250 ml of 1,2-
dichloroethane. The mixture is warmed at room temperature for a further 4
hours.
27.2 g (0.128 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added
and
the resultant mixture is warmed at 60°C for 2 hours. A further 18 g
(0.13 mol) of
anhydrous potassium carbonate are added and the mixture is warmed at
60°C for
a further 6 hours. The solvent is removed by distillation under a slight
vacuum (200
mbar) and replaced by xylene. 18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-
piperidyl)butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are
added,
the mixture is heated at reflux for 2 hours and, for a further 12 hours, the
water
formed during the reaction is removed by azeotropic distillation. The mixture
is
filtered. The solution is washed with water and dried over Na2S04. The solvent
is
evaporated and the residue is dried at 120-130°C in vacuo (0.1 mbar).
The desired
product is obtained as a colourless resin.
In general, the product (C-6) can for example be represented by a compound of
the formula (C-6-a), (C-6-[i) or (C-6-y). It can also be in the form of a
mixture of
these three compounds.
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HN (CHz) N (CHz) N - (CHz) - NH
2-12 ~ 2-12 ~ 2-12
N ~ N N' N N N
~N~N/R31 R31~N~~N~N/Ra1 R31~N~N~N/Rs1
HsC ~~ CHs HsC CHs H3C CH3 HsC ~ CHs H3C ~ CH3
H3C i CH3 H3C i CHs HsC i CH3 H3C ~ CHs H3C i CH3
R3z R3z Rsz R3z R3z b
(C-6-a)
HN (CHz) N
2-12
N~N
J, N ~ N ~ R31 (CHz)2-12
H3C ~ CH3 N (CHz)2-~2 N H
H3C N CH3
N~N N~N
R3z R31'N~N~N~R31 R31~N~N~N~R31
H3C ~ CH3 H3C ~ CH~3C ~ CH3 H3C ~ CH3
H3C N CH3 H3C N CH~-13C N CH3 H3C N CH3
- R3z R3z R3z R3z
5
(~-6-a>
(CHz)2-12
N ' N ( ~ Hz)2-12 ( ~ Hz)2-12
~N~N~R31 NH NH
H3C ~ CH3
N~N N~N
H3C N CH3R31\N~~N~N/Rs1 R31,N~N~N R
'' '\ / 31
R32
HsC ~ CH3 H3C ~ CHs H3C ~ CHI-13C ~~ CH3
H3C N CH H C N CH H C N CH C N CH
3 3 I 3 3 I ~3 I 3
- R3z R3z R3z R3z b
5
(C-6-y)
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A preferred meaning of the formula (C-6-a) is
HN (CH2)3 N (CH2)2 N - (CH2)3 NH
N~N CH-n n-HC N~N N~N
i a s s a ~ i C4H9 n n-H9C4 . i C4H9 n
N~ ~ ~ ~N~ I \ ~N~ /
N N N N N
H3C ~ CH3 H3C ~ CH3 H3C ~ CH3 H3C CH3 H3C CH3
N
H3C ~ CH3 H3C N CH3 H3C N CH3 H3C i CH3 H3C i CH3
H H H H
H b5
A preferred meaning of the formula (C-6-~3) is
HN (CHZ)3 N
N~N I
~.~ N :' N ~ C4H9 n ( ~ H22
H3C ~ CH3 N (CHZ)3 N H
N
H3C ~ CH3 N ~ N C H -n n-H C N ~ N
H n-HsC4 \ N ~ N ~ N/ a s s a1N 1 N " / C4Hs n
~N
H3C ~ CH3 H3C ~ CH3 H3C ~ CH3H3C ~ CH3
H3C N CH3 H3C N CH3 H3C i CH3H3C N CH3
H H H H
- b5
A preferred meaning of the formula (C-6-'y) is
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N (CH2) N
2
N ~ N (IH2)3 (IH2)3
N ~ / CaHe n
N NH NH
H3C ~ CH3 n-H C N ~ N CaH9 n n-H9Ca N ~ N
H3C i CH3 s a~N~~N~N~ N~N~ C4H9n
H N
H3C ~ CH3 H3C ~ CH3 H3C ~ CH3 H3C ~ CH3
H3C i CH3 H3C i CH3 H3C i CH3 H3C N CH3
H H H H b
In the above formulae (C-6-a) to (C-6-'y), b5 is preferably 2 to 20, in
particular 2 to 10.
Component (III) is for example TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM),
FERRO AM 806 (RTM), DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765
(RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), ADK STAB LA 52 (RTM), ADK
STAB LA 57 (RTM), ADK STAB LA 62 (RTM), ADK STAB LA 67 (RTM),
HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM),
DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM),
SANDUVOR PR 31 (RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150
(RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 x 128 (RTM), UVINUL
4050 H (RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM),
CYASORB UV 3346 (RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM),
CHIMASSORB 119 (RTM), UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL
2000 (RTM), UVINUL 5050 H (RTM), LICHTSCHUTZSTOFF UV 31 (RTM),
LUCHEM HA B 18 (RTM), ADK STAB LA 63 (RTM), ADK STAB LA 68 (RTM),
UVASORB HA 88 (RTM).
The meanings of the terminal groups which saturate the free valences in the
compounds of
the formulae (A-1 ), (A-2-a), (A-2-b), (A-4), (C-1 ), (C-3), (C-4), (C-5), (C-
6-a), (C-6-~) and
(C-6-y) depend on the processes used for their preparation. The terminal
groups can also be
modified after the preparation of the compounds.
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If the compounds of the formula (A-1 ) are prepared, for example, by reacting
a compound of
the formula
H3C CH3
HO N-CH2 ~H-OH
H3C CH3 Ai
in which A, is hydrogen or methyl, with a dicarboxylic acid diester of the
formula
Y-OOC-A2-COO-Y, in which Y is, for example, methyl, ethyl or propyl, and A2 is
as defined
above, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-
yl radical is
hydrogen or -CO-A2-COO-Y, and the terminal group bonded to the diacyl radical
is -O-Y or
H3C CH3
O N-CH2 i H-OH
H3C CH3 Ai
In the compounds of the formula (A-2-a), the terminal group bonded to the
nitrogen can be,
for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene
radical can
be, for example, a
CHZ
(CHZ) ~ ~-N
CH2 O O
H3C I /CH3
HsC N CH3
H
group.
In the compounds of the formula (A-2-b), the terminal group bonded to the
dimethylene
radical can be, for example, -OH, and the terminal group bonded to the oxygen
can be, for
example, hydrogen. The terminal groups can also be polyether radicals.
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In the compounds of the formula (A-4), the end group bonded to the -CHZ-
residue can be,
for example, hydrogen and the end group bonded to the -CH(C02A,) residue can
be, for
example, -CH=CH-COOA~.
If the compounds of the formula (C-1 ) are prepared by reacting a compound of
the formula
X~N~X
N ~ ~ ~N
R5
Ra
in which X is, for example, halogen, in particular chlorine, and R4 and R5 are
as defined
above, with a compound of the formula
H I R2 I H
R~ R3
in which R,, R2 and R3 are as defined above, the terminal group bonded to the
diamino
radical is hydrogen or
~N~X
N~ N
Rs
Ra
and the terminal group bonded to the triazine radical is X or
R2 ~ H
R1 R3
If X is halogen, it is advantageous to replace this, for example, by -OH or an
amino group
when the reaction is complete. Examples of amino groups which may be mentioned
are
pyrrolidin-1-yl, morpholino, -NH2, -N(C1-C8)alkyl)2 and -NR(C,-Cealkyl), in
which R is
hydrogen or a group of the formula (c-I).
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The compounds of the formula (C-1 ) also cover compounds of the formula
Rs* Rs*
~N~N~ i RZ N ~ ~ i Rz i N~Nv
* Nw N ~ N\ N N\/N R4*
Ra ~ R~ R3 ~ R, R3
N
N ~N~
R/ ~R * Ra \Rs R * R
4 5 b 4 s
i
wherein R,, R2, R3, R4, RS and b, are as defined above and RQ* has one of the
meanings of
R4 and RS* has one of the meanings of R5.
One of the particularly preferred compounds of the formula (C-1) is
c4~ ~c4
'~N~Ny C~)6-N NON-~a"~)6-N N1---N
N~ N N. N b N. N
1-l3C N ~ CI-t~ ~C N CFi~ ~C i ~ ~"i~C N Cf-L3
H
N - Ca~ ~Ca - N H ~Ca - N
r'4~
Calls
H3C N CI-h
i
H
The preparation of this compound is described in Example 10 of US-A-6,046,304.
In the compounds of the formula (C-3), the terminal group bonded to the
silicon atom can be,
for example, (R,4)3Si-O-, and the terminal group bonded to the oxygen can be,
for example,
-Si(R,a)3.
The compounds of the formula (C-3) can also be in the form of cyclic compounds
if b2 is a
number from 3 to 10, i.e. the free valences shown in the structural formula
then form a direct
bond.
In the compounds of the formula (C-4), the terminal group bonded to the 2,5-
dioxopyrrolidine
ring is, for example, hydrogen, and the terminal group bonded to the -
C(R23)(R2a)- radical is,
for example,
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or
O I O n N ~,
Rzz
R~8
In the compounds of the formula (C-5), the terminal group bonded to the
carbonyl radical is,
for example,
H3C CH3
O Rso
H3C CH3
and the terminal group bonded to the oxygen radical is, for example,
HsC CHa
C-RZS ~H R28 ~H-R2~ C-O N-R3o
O H3C CH3
In the compounds of the formulae (C-6-a), (C-6-~) and (C-6-'y), the terminal
group bonded to
the triazine radical is, for example, CI or a
HsC CHs
N-R3z
Rsi H3C CH3
group, and the terminal group bonded to the amino radical is, for example,
hydrogen or a
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N-/ _ N
R3'wN~N~N~Rs~
H3C ~CH3 H3C I/CH3
H3C N CH3 H3C N~CH3
R3z Raz
group.
According to a preferred embodiment
A, is hydrogen or methyl,
A2 is a direct bond or C2-Csalkylene, and
n, is a number from 2 to 25;
n2 and n2* are a number from 2 to 25;
A3 and A4 independently of one another are hydrogen or C,-C4alkyl, or A3 and
A4 together
form a C9-C,3alkylene group, and
the variables n3 independently of one another are a number from 1 to 25;
n4 is a number from 2 to 25,
A5 and A6 independently of one another are C,-C4alkyl, and
A, is C,-C4alkyl or a group of the formula (a-I)
with the proviso that at least 50 % of the radicals A~ are a group of the
formula (a-I);
m, is 1, 2 or 4,
if m, is 1, E2 is C,2-C2oalkyl,
if m, is 2, E2 is Cz-C,oalkylene or a group of the formula (b-I),
E3 is C,-C4alkyl,
EQ is C,-Csalkylene, and
E5 and E6 independently of one another are C,-C4alkyl, and
if m, is 4, EZ is C4-Cealkanetetrayl;
two of the radicals E, are -COO-(C,o-C,Salkyl), and
two of the radicals E, are a group of the formula (b-II);
E9 and E,o together form C9-C,3alkylene,
E" is hydrogen or a group -Z,-COO-Z2,
Z, is C2-Csalkylene, and
Z2 is C,o-C,salkyl;
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E,4 is hydrogen, and
E,5 is C2-Csalkylene or C3-CSalkylidene;
E" is C,o-C,4alkyl;
E24 is C,-C4alkoxy;
m2 is 1, 2 or 3,
when m2 is 1, E26 is a group -CH2CH2 NH-O ,
when m2 is 2, Ezs is C2-Cfialkylene, and
when m2 is 3, E26 is a group of the formula (b-IV)
the radicals E2, independently of one another are CZ-Csalkylene, and
the radicals E28 independently of one another are C,-C4alkyl or CS-
Cecycloalkyl; and
E3o is C2-Csalkylene;
R, and R3 independently of one another are a group of the formula (c-I),
R2 is CZ-Cealkylene,
R4 and RS independently of one another are hydrogen, C,-C,2alkyl, C5-
Cecycloalkyl or a
group of the formula (c-I), or the radicals R4 and R5, together with the
nitrogen atom to which
they are bonded, form a 5- to 10-membered heterocyclic ring, and
b, is a number from 2 to 25;
R, and R" independently of one another are hydrogen or C,-C4alkyl,
Re, R9 and R,o independently of one another are C2-C4alkylene, and
X,, X2, X3, X4, X5, X6, X, and Xe independently of one another are a group of
the formula
(c-II),
R,Z is hydrogen, C,-C4alkyl, C5-Cecycloalkyl or a group of the formula (c-I);
R,4 is C,-CQalkyl,
R,5 is C3-Csalkylene, and
bz is a number from 2 to 25;
R" and R2, independently of one another are a direct bond or a group
-N (X9)-CO-X, o-CO-N (X" )-,
X9 and X" independently of one another are hydrogen or C,-C4alkyl,
X,o is a direct bond,
R,9 and R23 are C,-CzSalkyl or phenyl,
R2o and R24 are hydrogen or C,-C4alkyl,
R22 is C,-C25alkyl or a group of the formula (c-I), and
b3 is a number from 1 to 25;
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RzS, R26, R2,, R28 and R29 independently of one another are a direct bond or
C,-C4alkylene, and
b4 is a number from 1 to 25;
b'S, b"5 and b"'S independently of one another are a number from 2 to 4, and
R3, is hydrogen, C,-C4alkyl, CS-C8cycloalkyl, phenyl or benzyl.
A non-agricultural article of interest is one wherein
component (III) is one or more sterically hindered amine compounds selected
from the group
consisting of the compounds of the formulae
(A-1-a), (A-2-a), (A-2-b), (A-3-a), (A-4-a),
(B_1 _a)~ (B_1 _b), (B_1 _c), (B_1 _d)~ (B_2_a), (B_3_a)~ (B_3_b)~ (B_4_a),
(B_4_b), (B_5)~ (B_6-a),
(B-~), (B-8-a), (B-9-a), (B-9-b)~ (B-9w)~ (B-10-a),
(C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a), (C-4-b), (C-4-
c) and (C-5-a) and a
product (C-6-a);
H3C CH3
O ~N-CHZ CH2 OOC-CHZCHZ CO (A-1-a)
H3C ~CH3
n1
wherein n, is a number from 2 to 20;
H3C CHs CH
z
O /(CHz)s
CHZ CH-CH2 N CHz (A-2-a)
~N
OH H3C CH3 IIO
n2
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i H-CHz O
HZ
/CHZ
(CHz)s ~ N
~CHZ O O
H3C CH3 (A-2-b)
HsC ~ ~CH3
H
- n2
wherein n2 and n2* are a number from 2 to 20;
CHz -(CHZ)s
H3C CHI ~ I CHZ-(CH2)o
O CH2 HaC CH I3
H N O~CHZ
N - CHZ - H-CHZ N O HaC CH3 OH O H3C CH3
H C ~ N - CHZ -CH-CHZ N
a CH3 O
OH H C N CHZ CH- CHZ- N
3 CHI O OH CH2 - I~~ N H
n3 ~ H3C CHI CHz O
HOC CHI
(CHZ)e CHz (CH2)9 CH2 n3
(A-3-a)
wherein the variables n3 independently of one another are a number from 1 to
20;
Ha
CH2 ~-CH2-~H (A-4-a)
I=o ~-o
CH3
A' n4
wherein n4 is a number from 2 to 20, and
at least 50 % of the radicals A, are a group of the formula (a-I)
H3C CH3
~N-Ae (a-I )
H3C CH3
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wherein A8 is hydrogen, C~-Cealkyl, O', -OH, -CH2CN, C,-C,Balkoxy, CS-
C,Zcycloalkoxy,
C3-Csalkenyl, C,-C9phenylalkyl unsubstituted or substituted on the phenyl by
1, 2 or 3
C,-C4alkyl; or C,-CBacyl,
and the remaining radicals A, are ethyl;
HaC CHs
O
E~ N O-C-(C~5-C~~alkyl) (B-1-a)
H3C ~CH3
H3C CH3 H3C CH3
O O
E~ N O-C-(CHZ)e C-O N-E~ (B-1-b)
H3C ~CH3 H3C CH3
H3C CH3 O C H C(CH3)a
4 9
E~-N O-~ I ~ CH2 ~ ~ OH
(B-1-c)
H3C CH3 C(CH3)3
2
H2C CH CH CH2 (B-1-d)
C=O C=O C=O C=O
O O O O
HsC N ~ CH3H3C N ~CH3 HaC N ~ CHsHaC ~ CH3
H3C I CH3 H3C I CH3 H3C ( CH3 H3C i CH3
E~ E~ E~ E~
wherein E, is hydrogen, C,-CBalkyl, O', -OH, -CH2CN, C,-C,ealkoxy, CS-
C,2cycloalkoxy,
C3-Csalkenyl, C,-C9phenylalkyl unsubstituted or substituted on the phenyl by
1, 2 or 3
C,-C4alkyl; or C,-CBacyl;
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H2 ~ ~ H ~ H ~ HZ (B 2 a)
E~ E~ E~ E~
in which two of the radicals E, are -COO-C,3H2, and
HsC CHs
two of the radicals E, are COO ~N - E8 and E8 has one of the meanings
H3C CH3
of E~;
/CH2 H
( ~)s ~N~ (B-3_a)
CHZ O C=O
H3C I /CH3
HsC I CH3
E, 2
O
/CH\Z /CH2CH2 CI-O-(C~2 C~4alkyl) (B-3-b)
C \)s ~N
CH/z ~O C=O
H3C I /CH3
HsC I CH3
E, 2
wherein E12 has one of the meanings of E~;
H3C CH3 H O H H3C CH3
E~3-N N-CH2CH2-C-N N-E~3 (B-4-a)
H3C CH3 H3C CH3
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H3C CH3 ~ ~ H ~ ~ i H3C CH3
3
E13-N N-C-C-N N-E~3 (B-4-b)
CH3
H3C CH3 H3C CH3
wherein E,3 has one of the meanings of E,;
H3C CHs
O
N ~ .N - Eis (B_5)
H3C CH3 N
N H3C CH3
Eis N NON
O
HsC CHs
wherein E,s has one of the meanings of E,;
H C O H3C CH3
25 12
.N N-Eia (B_6_a)
v v
O H3C CH3
wherein E,$ has one of the meanings of E,;
0
~Ez~
N N (B 7)
O'/ N \'
O
Ezo
in which E,9, E2o and E2, independently of one another are a group of the
formula (b-III)
H3C CH3
CHZ i H-CHZ NH N-Ez2 (b-III)
OH
H3C CH3
wherein E22 has one of the meanings of E,
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O HaC CHa
C-O N-Eza
HaC CHa
H3C0 ~ ~ CH - C (B-8-a)
HaC CHa
C-O N-E2a
O HaC CHa
wherein E23 has one of the meanings of E,;
H3C CHa
\~,~0
Ez5 N N -CHZCHZ NH (B-9-a)
HsC CHa
H3C CHa H3C
~~~0 O %~CHs
E25 N ~---~N -CH2CH2 N-E25 (B-9-b)
HsC CHa HsC CHa
HaC CHa O O HaC CHa
E25 N N-CHZCHz N N-CHZCHZ N N-E2s (B-9-C)
\'~/N
~ i
HaC' \ ~ I H3C CH
CHa N ~ N a
H\, aC _CHa
N-CH2CH2 N, .N-E2s
\H'sC'~/CHa
wherein E25 has one of the meanings of E,;
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O O
H3C CH3 ~ ~ ~ ~ H3C CH3
CH CH
E29 - N N - (CH2)e - N N E29 (B-10-a)
H3C CH3 H3C CH3
wherein E29 has one of the meanings of E~;
(C-1-a)
~" i Ha C(Ha
i - ~ -CHZ I~-CH3
H CH3 CH3 b
(CHz)s N
N~ N
H3C CH3 ~ ~ HaC CH3
3 HsC N CHa ~ vN_Rs
Rs
C4H9 H3C CH3 b
i
N
(CHZ)s N~ (C
l ~~ _ ~~
3 H3C
3 H.,C
J
b~
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(CHZ)s N~~ ( - )
C-1 d
N~ N
H3C CH3
H3C N CH3 N
C~
O b
,
wherein b, is a number from 2 to 20 and R6 is hydrogen, C,-CBalkyl, O', -OH, -
CH2CN,
C,-C,salkoxy, C5-C,zcycloalkoxy, C3-Csalkenyl, C,-C9phenylalkyl unsubstituted
or substituted
on the phenyl by 1, 2 or 3 C,-C4alkyl; or C,-Ceacyl;
H-N ~cH2~ 3 N ~cH2~2 (C-2-a)
N/ II N/ N
HsC°~",~"i HsCa\ . . ~ .~ ~CaHs
~CHa HsCX CHs HsC~ CHs
N CH3 H3C N CH3 H3C N CH3
R, s R, s R, a
2
wherein R,3 has one of the meanings of R6,
Hs
si-o (C-3-a)
0
H3C ( /CH3
H3C i ~CH3
R, s
2
wherein b2 is a number from 2 to 20 and R,6 has one of the meanings of R6;
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H
H
O N CHz ~ O N CHZ ~ (C-4-a)
~~H2~17-21 O ~~H2~17-21
CH3 CH3
H3C 1 /CH3 H3C CH3
H3C i CH3 H3C i CH
3
- R,a R,s b3
C' 3
CH -C (C-4-b)
O N O
H3C / /CH3
H3C i CH3
- R,a b
3
H
I I
O N CH2 ~ O %~~CH2 ~ (C
I O ''i6H33 ~ O C16H33
IH (H
C=O
I
C=O
I
NH
H3C ' /CH3
~3- I vn3 H3C i CH3
R,e Rya b
3
wherein b3 is a number from 1 to 20 and R1$ has one of the meanings of R6;
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O O H3 O O CH3
I I CI-O-CHZ ~-~ >--- I -CHz o (C_5-a)
o 0
CH3 CH3
H30 R30
ba
wherein b4 is a number from 1 to 20 and R3o has one of the meanings of R6;
a product (C-6-a) obtainable by reacting a product, obtained by reaction of a
polyamine of
the formula (C-6-1-a) with cyanuric chloride, with a compound of the formula
(C-6-2-a)
H2N (CHZ)3 NH (CHZ)2 NH (CHZ)3 NH2 (C-6-1-a)
H-N-C4H9 (C-6-2-a)
HsC CHs
H3C i CH3
R~
in which R32 has one of the meanings of Rs.
According to a preferred embodiment component (III) is a compound of the
formula
(A-1-a), (A-2-a), (A-2-b),
(B_1 _a), (B_1 _b), (B_1 _c)~ (B_1 _d), (B_2_a), (B_3_a), (B_3_b), (B-4_a),
(B_4_b), (B_5), (B_6_a)~
(B-8-a), (B-9-b), (B-10-a),
(C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a) or (C-5-a) or a
product (C-6-a).
According to a particular preferred embodiment component (III) is a compound
of the formula
(A-1-a), (A-2-a), (A-2-b),
(C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a) or (C-5-a) or a
product (C-6-a).
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A non-agricultural article which is of interest contains as component (III)
two different
sterically hindered amine compounds selected from the group consisting of the
compounds
of the formulae
(A-1-a), (A-2-a), (A-2-b), (A-3-a), (A-4-a),
(B_1 _a), (B_1 _b)~ (B_1 _c). (B_1 _d). (B_2_a)~ (B_3_a)~ (B_3_b)~ (B_4_a)~
(B_4_b)~ (B_5)~ (B_6_a)~
(B-~), (B-$-a)~ (B-9-a)~ (B-9-b), (B-9-c), (B-1~-a),
(C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a), (C-4-b), (C-4-
c) and (C-5-a) and a
product (C-6-a);
with the proviso that the two different sterically hindered amine compounds
are not selected
from the same generic formula.
Component (III) is particularly preferred a compound of the formula (A-1-a),
or
a compound of the formula (C-1-a) wherein R6 is hydrogen, or
a combination of a compound of the formula (A-1-a) with a compound of the
formula (C-1-a)
wherein R6 is hydrogen, or
a combination of a compound of the formula (A-1-a) with a compound of the
formula (C-2-a)
wherein R,3 is methyl, or
a combination of a compound of the formula (B-1-b) wherein E, is hydrogen with
a
compound of the formula (C-1-a) wherein R6 is hydrogen.
Component (II) is preferably a C2-C24carboxylate of Fe, Ce, Co, Mn, Cu or Vd,
in particular
Ce, Co or Mn.
C,o-CZOalkanoates of Ce, Co or Mn or Coo-C2oalkenoates of Ce, Co or Mn are of
particular
interest.
Examples of component (II) are stearates, oleates, linoleates, linolenates,
neodecanoates,
behenates, myristates, erucates and naphthenates of Fe, Ce, Co, Mn, Cu or Vd.
A particular preferred embodiment relates to stearates of Ce, Co or Mn.
Examples of component (I) are
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1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, po-
lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or
polybutadiene,
as well as polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene
(which optionally can be crosslinked), for example high density polyethylene
(HDPE), high
density and high molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh
molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE),
low
density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE)
and
(ULDPE).
Polyolefins, i.e, the polymers of monoolefins exemplified in the preceding
paragraph, prefe-
rably polyethylene and polypropylene, can be prepared by different, and
especially by the
following, methods:
a) radical polymerisation (normally under high pressure and at elevated
temperature).
b) catalytic polymerisation using a catalyst that normally contains one or
more than one
metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals
usually have
one or more than one ligand, typically oxides, halides, alcoholates, esters,
ethers,
amines, alkyls, alkenyls and/or aryls that may be either ~- or a-coordinated.
These
metal complexes may be in the free form or fixed on substrates, typically on
activated magnesium chloride, titanium(III) chloride, alumina or silicon
oxide. These
catalysts may be soluble or insoluble in the polymerisation medium. The
catalysts
can be used by themselves in the polymerisation or further activators may be
used,
typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl
oxides or metal
alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the
Periodic
Table. The activators may be modified conveniently with further ester, ether,
amine
or silyl ether groups. These catalyst systems are usually termed Phillips,
Standard
Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site
catalysts
(SSC).
2. Mixtures of the polymers mentioned under 1 ), for example mixtures of
polypropylene with
polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,
PP/LDPE) and
mixtures of different types of polyethylene (for example LDPE/HDPE).
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3. Copolymers of monoolefins and diolefins with each other or with other vinyl
monomers,
for example ethylene/propylene copolymers, linear low density polyethylene
(LLDPE) and
mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,
ethylene/hexene copo-
lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene
copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin
copolymers (e.g.
ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-
olefin is gene-
rated in-situ; propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/vi-
nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate
copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid
copolymers and their
salts (ionomers) as well as terpolymers of ethylene with propylene and a diene
such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such
copolymers
with one another and with polymers mentioned in 1 ) above, for example
polypropylene/ethy-
lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA),
LDPE/ethylene-
acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random
polyal-
kylene/carbon monoxide copolymers and mixtures thereof with other polymers,
for example
polyamides.
4. Hydrocarbon resins (for example CS-C9) including hydrogenated modifications
thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.) - 4.) may have any stereostructure
including syndio-
tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are
preferred. Stereoblock
polymers are also included.
5. Polystyrene, polyp-methylstyrene), poly(a-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers
including
styrene, a-methylstyrene, all isomers of vinyl toluene, especially p-
vinyltoluene, all isomers of
ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl
anthracene, and
mixtures thereof. Homopolymers and copolymers may have any stereostructure
including
syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are
preferred. Ste-
reoblock polymers are also included.
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6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers
selec-
ted from ethylene, propylene, dienes, nitrites, acids, malefic anhydrides,
maleimides, vinyl
acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/bu-
tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers),
styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,
styrene/maleic anhy-
dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength
of styrene copo-
lymers and another polymer, for example a polyacrylate, a diene polymer or an
ethylene/pro-
pylene/diene terpolymer; and block copolymers of styrene such as
styrene/butadiene/sty-
rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or
styrene/ethylene/propy-
lene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers
mentioned
under 6.), especially including polycyclohexylethylene (PCHE) prepared by
hydrogenating
atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers
mentioned
under 6a.).
Homopolymers and copolymers may have any stereostructure including
syndiotactic, isotac-
tic, hemi-isotactic or atactic; where atactic polymers are preferred.
Stereoblock polymers are
also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or a-
methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acry-
lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on
polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and malefic
anhydride on
polybutadiene; styrene, acrylonitrile and malefic anhydride or maleimide on
polybutadiene;
styrene and maleimide on polybutadiene; styrene and alkyl acrylates or
methacrylates on
polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene
terpolymers; styrene
and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene
and acrylonitrile on
acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers
listed under
6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
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8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers,
chlorinated
and brominated copolymer of isobutylene-isoprene (halobutyl rubber),
chlorinated or sulfo-
chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene,
epichlorohydrin
homo- and copolymers, especially polymers of halogen-containing vinyl
compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,
polyvinylidene fluoride,
as well as copolymers thereof such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a,(3-unsaturated acids and derivatives thereof such
as polyacry-
lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacryloni-
triles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with
other unsatu-
rated monomers, for example acrylonitrile/ butadiene copolymers,
acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide
copolymers or acry-
lonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl
derivatives or ace-
tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl
stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as
well as their copolymers with olefins mentioned in 1 ) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols,
polyethy-
lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which
contain
ethylene oxide as a comonomer; polyacetals modified with thermoplastic
polyurethanes,
acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides
with styrene
polymers or polyamides.
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15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or
polybutadi-
enes on the one hand and aliphatic or aromatic polyisocyanates on the other,
as well as
precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids
and/or from
aminocarboxylic acids or the corresponding lactams, for example polyamide 4,
polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12,
aromatic polyamides
starting from m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or
without an ela-
stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene
terephthalamide or poly-
m-phenylene isophthalamide; and also block copolymers of the aforementioned
polyamides
with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or
with polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene
glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and
polyamides
condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids,
polyhydantoins
and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic acids
or the corresponding lactones, for example polyethylene terephthalate,
polybutylene tereph-
thalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and
polyhydroxybenzoates, as well as block copolyether esters derived from
hydroxyl-terminated
polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polyketones.
21. Polysulfones, polyether sulfones and polyether ketones.
22. Crosslinked polymers derived from aldehydes on the one hand and phenols,
ureas and
melamines on the other hand, such as phenol/formaldehyde resins,
urea/formaldehyde re-
sins and melamine/formaldehyde resins.
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23. Drying and non-drying alkyd resins.
24. Unsaturated polyester resins derived from copolyesters of saturated and
unsaturated
dicarboxylic acids with polyhydric alcohols and vinyl compounds as
crosslinking agents, and
also halogen-containing modifications thereof of low flammability.
25. Crosslinkable acrylic resins derived from substituted acrylates, for
example epoxy acry-
lates, urethane acrylates or polyester acrylates.
26. Alkyd resins, polyester resins and acrylate resins crosslinked with
melamine resins, urea
resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,
heterocyclic or aromatic
glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and
bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or amines, with or
without
accelerators.
28. Natural polymers such as cellulose, rubber, gelatin and chemically
modified homologous
derivatives thereof, for example cellulose acetates, cellulose propionates and
cellulose
butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins
and their
derivatives.
29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM,
Poly-
amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA,
PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP,
PA/PPO, PBT/PC/ABS or PBT/PET/PC.
Component (I) is preferably a synthetic polymer, in particular from one of the
above groups.
Polyolefins are preferred and polyethylene, polypropylene, a polyethylene
copolymer or a
polypropylene copolymer are particularly preferred.
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According to a further preferred embodiment, component (I) is a polyolefin
homo- or
copolymer, a starch modified polyolefin, a starch based polymer composite or a
biopolymer.
According to another preferred embodiment component (1) is a biopolymer
selected from the
group consisting of polycaprolactone, polylactic acid, polyglycolic acid,
polyhydroxybutyrate-
valerate, polybutylene succinate, polyvinyl alcohol, polyhydroxyalcanoate and
polyethylene
adipate.
The non-agricultural article of this invention may contain further one or more
conventional
additives. Examples are
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-
tert-butyl-4,6-di-
methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-
butylphenol, 2,6-di-tert-bu-
tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-
4,6-dimethyl-
phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-
butyl-4-meth-
oxymethylphenol, nonylphenols which are linear or branched in the side chains,
for example
2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-
dimethyl-6-(1'-
methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and
mixtures there-
of.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-
butylphenol, 2,4-dioctyl-
thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-
dodecylthiomethyl-4-
nonylphenol.
1.3. Hydroauinones and alkylated hydropuinones, for example 2,6-di-tert-butyl-
4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-
diphenyl-4-octade-
cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-
hydroxyanisole, 3,5-di-tert-bu-
tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-
tert-butyl-4-hy-
droxyphenyl) adipate.
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1.4. Tocoaherols, for example a-tocopherol, ~3-tocopherol, ~y-tocopherol, 8-
tocopherol and
mixtures thereof (vitamin E).
1.5. H dy roxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-
4-methylphenol),
2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tent-butyl-3-methylphenol), 4,4'-
thiobis(6-tert-butyl-2-
methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-
hydroxyphenyl)-
disulfide.
1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-
methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-
methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-
nonyl-4-
methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-
ethylidenebis(4,6-di-tert-butyl-
phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-
methylenebis[6-(a-methylben-
zyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol],
4,4'-methy-
lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-
methylphenol), 1,1-bis(5-tert-
butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tent-butyl-5-methyl-2-
hydroxybenzyl)-4-
methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-
bis(5-tert-butyl-4-
hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-
bis(3'-tert-
butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-
phenyl)dicyclopenta-
diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-
methylphenyl]terephtha-
late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-
4-hydroxyphe-
nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-
dodecylmercaptobutane,
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-. N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-
4,4'-dihydroxydi-
benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-
4-hydroxy-
3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-
hydroxybenzyl)amine, bis(4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-
butyl-4-hydroxy-
benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-
butyl-2-hy-
droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-
methylbenzyl)malonate, di-
dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-
(1,1,3,3-te-
tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
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1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris(3,5-di-tert-
butyl-4-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-
2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-
butyl-4-hydroxy-
anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyanilino)-1,3,5-tri-
azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-
triazine, 2,4,6-tris-
(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-
butyl-4-hydroxyben-
zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)isocyanurate, 2,4,6-tris-
(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-
tert-butyl-4-hydroxy-
phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-
hydroxybenzyl)iso-
cyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-
hydroxybenzylphospho-
nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-
tert-butyl-4-hy-
droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-
methylbenzylphosphonate,
the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-
hydroxybenzylphosphonic acid.
1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-
hydroxystearanilide, octyl N-
(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of a-(3.5-di-tert-butyl-4-hydrox~iphenyl)propionic acid with mono-
or polyhydric
alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-
hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethy-
lene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hy-
droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylol
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of a-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,
octadecanol, 1,6-hexanedi-
ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-
(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol, trimethyl-
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olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo(2.2.2]octane; 3,9-
bis[2-{3-(3-tert-
butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-
tetraoxaspiro[5.5]-
undecane.
1.15. Esters of Q-(3.5-dic~rclohexyl-4-hydroxyahenLrl)propionic acid with mono-
or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, tri-
ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hy-
droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3.5-di-tert-butyl-4-hydroxyahenyl acetic acid with mono- or
polyhydric alco-
hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hy-
droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of~3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-
bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-
butyl-4-hydroxy-
phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hy-
drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-
hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau-
gard~XL-1, supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-bu-
tyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-
bis(1-ethyl-3-
methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicy-
clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-
naphthyl)-p-
phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-
dimethylbutyl)-N'-phe-
nyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-
cyclohexyl-N'-
phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-
N,N'-di-
sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-
isopropoxydiphenyl-
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amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-
phenyl-2-naph-
thylamine, octylated diphenylamine, for example p,p'-di-tert-
octyldiphenylamine, 4-n-butyl-
aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-
dodecanoylaminophenol, 4-
octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-
dimethylamino-
methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetra-
methyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-
bis(phenyl-
amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-
phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-
octyldiphenyl-
amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of
mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyl-
diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines,
2,3-dihydro-
3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and
dialkylated tert-
butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-
octylphenothiazines,
N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-
bis(2,2,6,6-tetra-
methylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-
yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers
2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-
methylphenyl)benzo-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-
butyl-2'-hydroxyphe-
nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-
tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-methylphe-
nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole, 2-(2'-
hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-
hydroxyphenyl)benzotriazole,
2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-
butyl-2'-hydroxy-5'-
(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-
(2-ethylhexyl-
oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tent-butyl-2'-
hydroxy-5'-(2-meth-
oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbonyl-
ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonylethyl]-2'-hydroxy-
phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-
2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-
methylenebis[4-(1,1,3,3-
tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product
of 2-[3'-tert-bu-
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tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with
polyethylene glycol
300; ~R-CH2CHz COO-CHZCH2~- , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-
benzotri-
2
azol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-
tetramethylbutyl)phenyl]-
benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-
dimethylbenzyl)phenyl]ben-
zotriazole.
2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy,
4-decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-
dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-
butylphenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylben-
zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-
4-hydroxybenzo-
ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-
butyl-4-hydroxyben-
zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrvlates, for example ethyl a-cyano-[3,~-diphenylacrylate, isooctyl a-
cyano-~,~-diphe-
nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-~-methyl-p-
methoxycinna-
mate, butyl a-cyano-(3-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-
methoxycin-
namate and N-([i-carbomethoxy-[i-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[4-(1,1,3,3-
tetramethyl-
butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional
ligands such as n-
butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate,
nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-
hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-
methylphe-
nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole,
with or with-
out additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-
piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-
piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-
pentamethyl-4-piperi-
dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-
hydroxyethyl)-
2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic
condensates of
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N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-
octylamino-2,6-di-
chloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetra-
methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-
bis(3,3,5,5-tetrame-
thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethyl-
piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-
tert-butylbenzyl)-
malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-
dione, bis(1-octyl-
oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-
tetramethylpiperidyl)succi-
nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-
piperidyl)hexamethylene-
diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-
chloro-4,6-bis(4-n-
butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-
aminopropylamino)-
ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-
pentamethylpiperidyl)-
1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-
7,7,9,9-tetrame-
thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-
4-piperidyl)pyr-
rolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-
2,5-dione, a
mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a
condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-
cyclohexylamino-2,6-
dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and
2,4,6-tri-
chloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine
(CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-
triazine as well
as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg.
No.
[192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-
(1,2,2,6,6-
pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-
oxa-3,8-di-
aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-
cycloundecyl-1-oxa-
3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-
pentamethyl-4-
piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-
bis(2,2,6,6-tetrame-
thyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic
acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-
tetramethyl-4-
piperidyl)]siloxane, a reaction product of malefic acid anhydride-a-olefin
copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-
aminopiperidine.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-
ethoxy-2'-ethyloxanilide,
N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide
and its mixture
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with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-
disubstituted
oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hvdrox p~yl)-1,3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-
octyloxyphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-
(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-
hydroxy-4-propyl-
oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-
methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-
[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[2-
hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[4-
(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-
dimethylphenyl)-
1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-
bis(2,4-dimethyl-
phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-
triazine, 2-(2-hy-
droxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-
butoxy-2-hy-
droxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-
phenyl-
1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-
hydroxypropyloxy]phenyl}-4,6-bis(2,4-
dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-
salicyloyl hydrazine,
N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,
oxanilide, isophthaloyl
dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyl-
oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl
phosphites,
phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,
trioctadecyl phos-
phite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-di-
cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-
methylphenyl)pentaerythritol
diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-
methylphenyl)-
pentaerythritol diphosphite, bis(2,4,6-tris(tent-butylphenyl)pentaerythritol
diphosphite, tristea-
ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene
diphosphonite, 6-
isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,
bis(2,4-di-tert-
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butyl-6-methylphenyl)methyl phosphate, bas(2,4-di-tert-butyl-6-
methylphenyl)ethyl phosphate,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-
dioxaphosphocin, 2,2',2"-nitrilo-
[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-
ethylhexyl(3,3',5,5'-te-
tra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-
tert-butylphenoxy)-
1,3,2-dioxaphosphirane.
The following phosphates are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphate (Irgafos~168, Ciba-Geigy),
tris(nonylphenyl) phosphate,
(CH3)3C ~ C(CH3)3 (CH3)3C C(CH3)3
O \
\ \
(A) H3C-CH P-F P-O-CH2CH2 N (B)
O ~ O
/ I
(CH3)3C
C (CH3)3 C(CH3)3
(CH3)3C 3
C(CH3)3
(CH3)3C /
\ ~O
\
P-O-CH2CH(C4H9)CHZCH3
O
(CH3)3C \
C(CH3)s
O O
(CH3)3C / ~ O P\ ~P-O / ~ C(CH3)s (p)
O O
C(CH3)3 (CH3)3C
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C(CH3)3 (CH3)3C
O O
H3C ~ ~ O-P' ~P-O ~ ~ CH3
O O (E)
C(CH3)3 (CH3)3C
i Hs
H3C-C-CH3
O O
(F) H3~C~8 O-P ~P-O-C~8H3~ ~ O P-OCHzCH3 (G)
O O HsC
H CSC CH3
CH3
5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-
diethylhydroxylamine, N,N-
dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-
ditetradecylhydroxylamine, N,N-
dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-
octadecylhydrox-
ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from
hydrogenated tallow amine.
6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-
methylnitrone, N-octyl-
alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-
tridecylnitrone, N-
hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-
hexadecyl-al-
pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-
alpha-hepta-
decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-
dialkylhydroxyl-
amine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate or distearyl
thiodipropionate.
8. Peroxide scavengers, for example esters of (3-thiodipropionic acid, for
example the lauryl,
stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercapto-
benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide,
pentaerythritol tetrakis(~i-
dodecylmercapto)propionate.
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9. Polvamide stabilisers, for example copper salts in combination with iodides
and/or phos-
phorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,
dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali
metal salts and alkaline earth metal salts of higher fatty acids, for example
calcium stearate,
zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium
palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
11. Nucleating agents, for example inorganic substances, such as talcum, metal
oxides, such
as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of,
preferably,
alkaline earth metals; organic compounds, such as mono- or polycarboxylic
acids and the
salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic
acid, sodium succinate
or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
Especially
preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-
di(paramethyldibenzyli-
dene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
12. Fillers and reinforcing agents, for example calcium carbonate, silicates,
glass fibres,
glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and
hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural products,
synthetic fibers.
13. Other additives, for example plasticisers, lubricants, emulsifiers,
pigments, rheology
additives, catalysts, flow-control agents, optical brighteners, flameproofing
agents, antistatic
agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S.
4,325,863;
U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611;
DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-
acetoxyethoxy)-
phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-
stearoyloxyethoxy)phenyl]-
benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-
hydroxyethoxy]phenyl)benzofuran-2-one],
5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-
dimethylphenyl)-5,7-
di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-
tert-butylbenzo-
furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-
dimethylphe-
nyl)-5,7-di-tert-butylbenzofuran-2-one.
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A preferred non-agricultural article additionally contains an aliphatic poly
hydroxy-carboxyl
acid, in particular citric acid.
An aliphatic poly hydroxy-carboxyl acid is in particular an aliphatic acid
having either more
than one -OH or more than one -COOH group in the organic acid. Examples are
the
aliphatic, dihydroxy, monocarboxyl acids, such as glyoxylic acid and glyceric
acid; the
aliphatic, polyhydroxy, monocarboxyl acids, such as erythric acid, arabic acid
or mannitic
acid; the aliphatic, monohydric, dicarboxyl acids, such as tartronic acid or
malic acid; the
aliphatic, dihydroxy, dicarboxyl acids, such as tartaric acid; the aliphatic,
polyhydroxy,
dicarboxyl acids, such as trihydroxyglutaric acid and succharic acid; and the
aliphatic,
monohydroxy, tricarboxyl acids, such as citric acid.
A further preferred embodiment of this invention relates to a non-agricultural
article which
contains in addition one or more of the following components
(IV) an antioxidant,
(V) an UV absorber,
(VI) a filler,
(VII) a pigment,
(VIII) an inorganic or organic salt of Ca, Mg, Zn or AI.
Preferred antioxidants (component IV)) are those which are described above
under item 1.
Suitable examples of fillers (component (VI)) are those described above under
item 12.
Preferred fillers are inorganic or synthetic carbonates, nepheline syenite,
talc, magnesium
hydroxide, aluminum trihydrate, diatomaceous earth, mica, natural or synthetic
silica and
calcinated clay.
Examples of the UV absorber (component (V)) are a 2-(2'-
hydroxyphenyl)benzotriazole, a 2-
hydroxybenzophenone, an ester of substituted or unsubstituted benzoic acid, an
acrylate, an
oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or
a
formamidine.
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The 2-(2'-hydroxyphenyl)benzotriazole is e.g. 2-(2'-hydroxy-5'-methylphenyl)-
benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-
hydroxyphenyl)benzo-
triazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-
(3',5'-di-tert-butyl-
2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-
methylphenyl)-5-
chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole, 2-(2'-
hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-
hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-
(3'-tert-butyl-2'-
hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-
butyl-5'-[2-(2-
ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-
tert-butyl-2'-
hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-
butyl-2'--
hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-
octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonyl-
ethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-
methylphenyl)benzotri-
azole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'--
methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol] or the
transesterifica-
tion product of 2-[3'-tent-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-
2H-benzotri-
azole with polyethylene glycol 300; [R-CH2CH2-COO(CHz)s-12 where R = 3'-tert-
butyl-4'-
hydroxy-5'-2H-benzotriazol-2-ylphenyl.
2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-
butyl-2'-hydroxy-5'-
methylphenyl)-5-chloro-benzotriazole and 2-(3',5'-di-tert-amyl-2'-
hydroxyphenyl)-
benzotriazole are preferred.
The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy,
4-decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-
dimethoxy derivatives.
2-Hydroxy-4-octyloxybenzophenone is preferred.
The ester of a substituted or unsubstituted benzoic acid is for example 4-tert-
butyl-phenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylben-
zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-
4-hydroxybenzo-
ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-
butyl-4-hydroxy-
benzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-
hydroxybenzoate.
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2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-
di-tert-butyl-4-
hydroxybenzoate are preferred.
The acrylate is for example ethyl a-cyano-[i,(3-diphenylacrylate, isooctyl a-
cyano-~,~-di-
phenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-[i-methyl-p-
methoxy-
cinnamate, butyl a-cyano-[i-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-
p-
methoxycinnamate or N-((3-carbomethoxy-[i-cyanovinyl)-2-methylindoline.
The oxamide is for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-
ethoxy-2'-ethyloxanilide,
N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide
or its mixture
with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide or mixtures of ortho- and
para-methoxy--
disubstituted oxanilides or mixtures of o- and p-ethoxy-disubstituted
oxanilides.
The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example 2,4,6-tris(2-hydroxy-4-
octyloxyphenyl)--
1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-
(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-
hydroxy-4-propyl-
oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4-
methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-
[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[2-
hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-
triazine, 2-[4-
(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-
dimethylphenyl)--
1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-
bis(2,4-dimethyl-
phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-
triazine, 2-(2--
hydroxy-4-methoxyphenyl)-4,6-Biphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-
(3-butoxy-2--
hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-
methoxyphenyl)-6-phenyl-
1,3,5-triazine or 2-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-4,6-bis[4-
phenylphenyl]-1,3,5-
triazine.
2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-
(2-hydroxy-4-
hexyloxy)phenyl-4,6-Biphenyl-1,3,5-triazine and 2-[2-hydroxy-4-(2-
ethylhexyloxy)phenyl]-4,6-
bis[4-phenylphenyl]-1,3,5-triazine are preferred.
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The monobenzoate of resorcinol is for example the compound of the formula
0 off
The formamidine is for example the compound of the formula
/ ~ ~ C2H5
H5C20-C N=CH-N
The UV absorber is in particular a
2-(2'-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or a
hydroxyphenyltriazine.
The pigment (component (VII)) may be an inorganic or organic pigment.
Examples of inorganic pigments are titanium dioxide, zinc oxide, carbon black,
cadmium
sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and so on.
Examples of organic pigments are azo pigments, anthraquinones,
phthalocyanines,
tetrachloroisoindolinones, quinacridones, isoindolines, perylenes,
pyrrolopyrroles (such as
Pigment Red 254) and so on.
All pigments described in "Gachter/Muller: Plastics Additives Handbook, 3rd
Edition, Hanser
Publishers, Munich Vienna New York", page 647 to 659, point 11.2.1.1 to
11.2.4.2 can be
used as component (VII).
Particularly preferred pigments are titanium dioxide or carbon black,
optionally in combination
with an organic pigment.
Examples of such organic pigments are:
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C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95, C.I. Pigment
Yellow 138, C.I.
Pigment Yellow 139, C.I. Pigment Yellow 155, C.I. Pigment Yellow 162, C.I.
Pigment Yellow
168, C.I. Pigment Yellow 180, C.1. Pigment Yellow 183, C.I. Pigment Red 44,
C.I. Pigment
Red 170, C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red 254,
C.I. Pigment
Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3,
C.I. Pigment
Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Green 7, C.I. Pigment Blue 15:1,
C.I. Pigment
Blue 15:3 and C.I. Pigment Violet 19.
The organic salt of calcium, magnesium, zinc or aluminum defined in component
(VII) is
preferably a compound of the formula MeL2, in which Me is calcium, magnesium
or zinc, or a
compound of the formula AILS. L is an anion of an organic acid or of an enol.
The organic
acid can, for example, be a sulfonic acid, sulfinic acid, phosphonic acid or
phosphinic acid,
but is preferably a carboxylic acid. The acid can be aliphatic, aromatic,
araliphatic or
cycloaliphatic; it can be linear or branched; it can be substituted by
hydroxyl or alkoxy
groups; it can be saturated or unsaturated and it preferably contains 1 to 24
carbon atoms.
Examples of carboxylic acids of this type are formic, acetic, propionic,
butyric, isobutyric,
caprioic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic,
behenic, oleic, lactic,
ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic, 4-
dodecylbenzoic,
phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-
butylcyclohexanecarboxylic or
cyclohexylacetic acid. The carboxylic acid can also be a technical mixture of
carboxylic acids,
for example technical mixtures of fatty acids or mixtures of alkylated benzoic
acids.
Examples of organic acids containing sulfur or phosphorus are methanesulfonic,
ethanesulfonic, a,a-dimethylethanesulfonic, n-butanesulfonic, n-
dodecanesulfonic,
benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, 4-
dodecylbenzenesulfonic or
cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or
naphthalenesulfinic acid,
butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethyl
phenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acid or
diphenylphosphinic acid.
If L is an enolate anion, it is preferably an anion of a ~3-dicarbonyl
compound or of an
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o-acylphenol. Examples of (i-dicarbonyl compounds are acetylacetone,
benzoylacetone,
dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate
or
a-acetylcyclohexanone. Examples of o-acylphenols are 2-acetylphenol, 2-
butyroylphenol,
2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate is
preferably the anion
of a ~i-dicarbonyl compound having 5 to 20 carbon atoms.
Organic salts of zinc or magnesium are preferably an acetylacetonate or an
aliphatic
monocarboxylate having, for example, 1 to 24 carbon atoms. Magnesium acetate,
laurate
and stearate, zinc formate, acetate, oenanthate, laurate and stearate as well
as zinc
acetylacetonate and magnesium acetylacetonate are some of the particular
preferred
examples.
Zinc stearate, magnesium stearate, zinc acetylacetonate, magnesium
acetylacetonate, zinc
acetate and magnesium acetate are of special interest.
The inorganic salt of zinc, magnesium or aluminum is for example
a carbonate containing compound such as
~ Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g a Ca/Mg
carbonate such
as Microdol Super (RTM) from Micro Minerals (RTM); or
~ a natural or synthetic hydrotalcite.
The natural hydrotalcite is held to possess a structure Mg6Al2(OH)16C03 ~ 4
H20.
A typical empirical formula of a synthetic hydrotalcite is
AI2Mg4.3sOH11.3sC03(1.s7) ' x H20.
Examples of the synthetic product include:
Mgo.7Alo.3(OH)2(C03)o.ls ' 0.54 H20,
Mg4.5A12(OH)13C03 ' 3.5 H20, or
MgazAl(OH)l2.aC03.
Preferred synthetic hydrotalcites are L-55R II (RTM) from REHEIS (RTM) as well
as ZHT-4A
(RTM) and DHT-4A (RTM) from Kyowa Chemical Industry Co (RTM).
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Component (VII) can also be a mixture of two different Mg- and/or Zn-
compounds, for
example
~ Mg-stearate and hydrotalcite (DHT-4A (RTM)),
~ Zn-stearate and hydrotalcite (DHT-4A (RTM)),
~ Mg-acetylacetonate and hydrotalcite (DHT-4A (RTM)),
~ Mg-oxide and hydrotalcite (DHT-4A (RTM)),
~ Mg-hydroxide and hydrotalcite (DHT-4A (RTM)),
~ Zn-hydroxide-carbonate and Mg-stearate,
~ Zn-hydroxide-carbonate and Zn-stearate,
~ Zn-hydroxide-carbonate and Mg-acetylacetonate,
~ Zn-hydroxide-carbonate and Mg-oxide,
~ Zn-hydroxide-carbonate and Zn-oxide,
~ Zn-hydroxide-carbonate and Mg-hydroxide,
~ hydrotalcite (REHEIS (RTM)) and Mg-stearate,
~ hydrotalcite (REHEIS (RTM)) and Zn-stearate,
~ hydrotalcite (REHEIS (RTM)) and Mg-oxide,
~ dolomite (Microdol Super (RTM)) and Zn-stearate,
~ dolomite (Microdol Super (RTM)) and Mg-stearate,
~ dolomite (Microdol Super (RTM)) and Zn-oxide,
~ dolomite (Microdol Super (RTM)) and Mg-hydroxide,
~ Mg-stearate and Zn-stearate,
~ Mg-stearate and Zn-acetylacetonate,
~ Mg-stearate and Mg-oxide,
~ Mg-stearate and Zn-oxide,
~ Mg-stearate and Mg-hydroxide,
~ Zn-stearate and Mg-acetate,
~ Zn-stearate and Mg-oxide,
~ Zn-stearate and Mg-hydroxide,
~ Mg-acetylacetonate and Zn-acetylacetonate,
~ Mg-acetylacetonate and Mg-oxide,
~ Mg-acetylacetonate and Zn-oxide,
~ Mg-acetylacetonate and Mg-hydroxide,
~ Zn-acetylacetonate and Mg-oxide,
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~ Zn-acetylacetonate and Zn-oxide, or
~ Mg-oxide and Zn-oxide.
In this case, the two different compounds of component (VII) may be present in
a weight ratio
of 1:10 to 10:1.
According to a preferred embodiment of this invention component (VII) is
selected from the
group consisting of Mg carboxylates, Zn carboxylates, AI carboxylates, Mg
oxides, Zn oxides,
AI oxides, Mg hydroxides, Zn hydroxides, AI hydroxides, Mg carbonates, Zn
carbonates or AI
carbonates.
Preferred examples of component (VII) as an organic salt of Ca are
carboxylates such as
Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
Examples of component (VII) as an inorganic salt of Ca are CaO, Ca(OH)2,
CaC03, CaCl2,
CaF2, Ca3(P04)Z, CaHP04, Ca(P03)2, Ca2P20,, CaS04 and CaSio3.
According to another preferred embodiment of this invention component (VII) is
a Ca
carboxylate, a Mg carboxylate, a Zn carboxylate or a hydrotalcite.
Components (II) and (III) and optionally components (IV) to (VIII) may be
added to the
organic polymer either individually or mixed with one another.
Components (II) and (III) and optionally components (IV) to (VIII) are present
in the organic
polymer in an amount suitable to obtain a sufficient weathering resistance and
to initiate a
controlled degradation at a desired moment.
The possibility of lifetime control is fundamental for non-agricultural
articles. The article has
to keep its properties and its performance during the service and degradation
has to take
place when the function of the article is finished. Service lifetimes can vary
dramatically.
The main components being present in the organic polymer are one or more
prodegradant
additives (component (II)) and one or more stabilizers (components (III) to
(VIII)). By
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appropriately dosing the amount of prodegradant and the amount of stabilizer,
the required
service periods and time to disappearance can be obtained.
Component (II) may be present in the organic polymer in an amount of, for
example, 0.005 to
% or 0.005 to 5 %, preferably 0.005 to 1 %, in particular 0.03 to 0.4 %,
relative to the
weight of the organic polymer.
Component (III) may be present in the organic polymer in an amount of, for
example 0.01 to
% or 0.01 to 10 % or 0.01 to 5 %, preferably 0.01 to 1.5 %, in particular 0.05
to 1.2 %,
relative to the weight of the organic polymer.
Component (IV) may be present in the organic polymer in an amount of
preferably 0.005 to
1 %, in particular 0.01 to 0.3 %, relative to the weight of the organic
polymer.
Component (V) may be present in the organic polymer in an amount of preferably
0.01 to 5
%, in particular 0.1 to 2 %, relative to the weight of the organic polymer.
Component (VI) may be present in the organic polymer in an amount of
preferably 0.05 to 80
%, in particular 0.5 to 70 %, relative to the weight of the organic polymer.
Component (VII) may be present in the organic polymer in an amount of
preferably 0.05 to
40 %, in particular 0.5 to 30 %, relative to the weight of the organic
polymer.
Component (VIII) may be present in the organic polymer in an amount of
preferably 0.005 to
5 %, in particular 0.05 to 1 %, relative to the weight of the organic polymer.
The total amount of the components (III) to (VIII) being present in the
organic polymer is
preferably 0.15 to 90 %, in particular 1.2 to 80 %, relative to the weight of
the organic
polymer.
The weight ratio of the components (11):(111) may be for example 0.0003:1 to
1000:1 or
0.003:1 to 100:1, in particular 0.025:1 to 8:1.
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The weight ratio of the components (II):(IV) may be for example 0.005:1 to
200:1, in
particular 0.1:1 to 40:1.
The weight ratio of the components (II):(V) may be for example 0.001:1 to
100:1, in particular
0.01 5:1 to 4:1.
The weight ratio of the components (II):(VI) may be for example 0.0001:1 to
20:1, in
particular 0.0004:1 to 1.0:1.
The weight ratio of the components (II):(VII) may be for example 0.001:1 to
200:1, in
particular 0.015:1 to 8:1.
The weight ratio of the components (II):(VIII) may be for example 0.001:1 to
200:1, in
particular 0.015:1 to 8:1.
The above components can be incorporated into the organic polymer to be
stabilized in a controlled form by known methods, for example before or during
shaping or by applying the dissolved or dispersed compounds to the organic
polymer, if necessary with subsequent evaporation of the solvent. The
components can be added to the organic polymer in the form of a powder,
granules or a masterbatch, which contains these components in, for example, a
concentration of from 2.5 to 25 % by weight.
If desired, the components (II) and (III) and optionally (IV) to (VIII) can be
blended
with each other before incorporation into the organic polymer. They can be
added
to the polymer before or during the polymerization or before the crosslinking.
The main components of the present additive system are a prodegradant additive
(component (II)) and a weathering stabilizer (component (III)). By
appropriately dosing the
amount of the prodegradant and the amount of the weathering stabilizer, the
required service
periods and time to degradation and disappearance can be obtained. Examples of
typical life
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times of non-agricultural articles are 10 to 180 days, lifes up to 24 months
can also be
required and achieved.
Thus, a further preferred embodiment of the present invention is a non-
agricultural article
containing the components (I), (II) and (III) as defined above and having a
life time of 10 to
720 days.
The example below illustrates the invention in greater detail. All percentages
and parts are
by weight, unless stated otherwise.
Example 1:
Each compound of the list reported below is mixed via master batch, in a slow
mixer, with
low density polyethylene (LDPE) pellets (Riblene FF 29 (RTM), supplied by
Polimeri
Europa(RTM); characterized by a density of 0.921 g/cm3 and a melt flow index
of 0.60 at
190°C and 2.16 Kg), and with linear low density polyethylene (LLDPE)
pellets (Clearflex
FG308 (RTM), supplied by Polimeri Europa (RTM); characterized by a density of
0.924 g/cm3
and a melt flow index of 0.97 at 190°C and 2.16 Kg). The ratio
LDPE/LLDPE is 1:4.
The mixture is blown at 210°C and films of 12 and 25 microns thickness
are obtained.
The films are exposed outdoors in Pontecchio Marconi (Bologna, Italy). Total
irradiation in
the location is 110 Klys/year.
During the exposure, the films are periodically checked visually and the time
to start of
degradation (fessuration) and to embrittlement (= very fragile film = end of
the life time ) is
registered.
The results are indicated in Tables 1 to 4.
Table 1:
Films without pigment, 25 microns thick.
1:1 Mixture of
Cobalt StearateStabilizer (A-1-a)StabilizerDays to Days to
and
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Stabilizer (C-1-a-1)(A-1-a) fessurationembrittlement
Without Without Without 92 350
0.13 0.05 Without 39 67
0.13 Without 0.2 52 108
Table 2:
Films without pigment, 12 microns thick.
1:1 Mixture of
Cobalt StearateStabilizer (A-1-a)Days to Days to
and
Stabilizer (C-1-a-1)fessuration embrittlement
0.13 0.05 43 65
0.13 0.2 43 128
Table 3:
Films with 3 % of carbon black, 25 microns thick.
1:1 Mixture of
Cobalt StearateStabilizer (A-1-a)Days to Days to
and
Stabilizer (C-1-a-1)fessuration embrittlement
Without Without 120 410
0.13 0.6 57 79
Table 4:
Films with 3 % of carbon black, 12 microns thick.
1:1 Mixture of
Cobalt StearateStabilizer (A-1-a)Days to Days to
and
Stabilizer (C-1-a-1)fessuration embrittlement
0.13 0.2 36 57
0.13 0.6 53 75
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Stabilizer (A-1-a):
TINUVIN 622 (RTM)
H3C CH3
O 'N-CHz CH2 OOC-CH2CHZ CO (A-1-a)
H3C ~CH3
n~
wherein n, is a number from 2 to 20.
Stabilizer (C-1-a-1):
CHIMASSORB 944 (RTM)
N
N (CHZ)6 N ~ (C-1-a)
N~ N
H3C CH3 H3C CH3 ~ CH3 CH3
H3C H CH3 H3C N CH3 N- ~ -CHZ ~-CH3
H CH3 CH3 b
i
wherein b, is a number from 2 to 20.
